Membrane lipid profiles of coral responded to zinc oxide nanoparticle-induced perturbations on the cellular membrane.

Zinc oxide nanoparticles (nZnOs) released from popular sunscreens used during marine recreation apparently endanger corals; however, the known biological effects are very limited. Membrane lipids constitute the basic structural element to create cell a dynamic structure according to the circumstance. Nano-specific effects have been shown to mechanically perturb the physical state of the lipid membrane, and the cells accommodating the actions of nZnOs can be involved in the alteration of the membrane lipid composition. To gain insight into the effects of nanoparticles on coral, glycerophosphocholine (GPC) profiling of the coral Seriatopora caliendrum exposed to nZnOs was performed in this study. Increasing lyso-GPCs, docosapentaenoic acid-possessing GPCs and docosahexaenoic acid-possessing GPCs and decreasing arachidonic acid-possessing GPCs were the predominant changes responded to nZnO exposure in the coral. A backfilling of polyunsaturated plasmanylcholines was observed in the coral exposed to nZnO levels over a threshold. These changes can be logically interpreted as an accommodation to nZnOs-induced mechanical disturbances in the cellular membrane based on the biophysical properties of the lipids. Moreover, the coral demonstrated a difference in the changes in lipid profiles between intra-colonial functionally differentiated polyps, indicating an initial membrane composition-dependent response. Based on the physicochemical properties and physiological functions of these changed lipids, some chronic biological effects can be incubated once the coral receives long-term exposure to nZnOs.

Intra-Colonial Functional Differentiation-Related Modulation of the Cellular Membrane in a Pocilloporid Coral Seriatopora caliendrum.

Scleractinian corals have displayed phenotypic gradients of polyps within a single genotypic colony, and this has profound implications for their biology. The intrinsic polymorphism of membrane lipids and the molecular interactions involved allow cells to dynamically organize their membranes to have physicochemical properties appropriate for their physiological requirements. To gain insight into the accommodation of the cellular membrane during ontogenetic shifts, intra-colony differences in the glycerophosphocholine profiling of a pocilloporid coral, Seriatopora caliendrum, were characterized using a previously validated method. Specifically, several major polyunsaturated phosphatidylcholines showed higher levels in the distal tissue of coral branches. In contrast, the corresponding molecules with 1-2-degree less unsaturation and plasmanylcholines were expressed more highly in the proximal tissue. The lipid profiles of these two colonial positions also contrasted sharply with regard to the saturated, monounsaturated, and lyso-glycerophosphocholine ratios. Based on the biochemical and biophysical properties of these lipids, the associated modulation of cellular membrane properties could be related to the physiological requirements, including coral growth and aging, of the functionally differentiated polyps. In this study, the metabolic regulation of membrane lipids involved in the functional differentiation of polyps within a S. caliendrum colony was identified.

Norcembranoidal diterpenes from the cultured-type octocoral Sinularia numerosa.

A known norcembranoidal diterpene, 5-episinuleptolide (1), along with a new analogue, 4α-hydroxy-5-episinuleptolide (2), were isolated from a cultured-type soft coral Sinularia numerosa. The structures of 1 and 2 were elucidated on the basis of spectroscopic methods and by comparison of the data with those of the related metabolites. Cytotoxicity of metabolites 1 and 2 against a panel of tumor cells is also described. Compound 2 exhibited moderate cytotoxicity toward CCRF-CEM cells with an IC50 value 4.21 µg/mL. Preliminary SAR (structure activity relationship) information was obtained from these two compounds.

Determination of cholesterol and four phytosterols in foods without derivatization by gas chromatography-tandem mass spectrometry.

In this study, a method for determination of cholesterol and four phytosterols by gas chromatography coupled with electron impact ionization mode-tandem mass spectrometry without derivatization in general food was developed. The sample was saponified with 7.5% KOH in methanol. After heating on hot plate and reflux for 60 minutes, the saponified portion was extracted with n-hexane/petroleum ether (50:50, v/v). The extracts were evaporated with rotary evaporator and then redissolved with tetrahydrofuran. The tetrahydrofuran layer was transferred into an injection vial and analyzed by gas chromatography on a 30 m VF-5 column. Limit of quantification was 2 mg/kg. Recoveries of cholesterol and four phytosterols from general food were between 91% and 100%.

Cladieunicellin J, a new hydroperoxyeunicellin from cladiella sp.

A new 6-hydroperoxyeunicellin diterpenoid, designated as cladieunicellin J (1), was isolated from an octocoral Cladiella sp., and its structure elucidated by spectroscopic methods. Compound 1 was found to exhibit cytotoxicity toward CCRF-CEM human T-cell acute lymphoblastic leukemia.

Cladieunicellins M-Q, new eunicellins from Cladiella sp.

Five new 7α-hydroxyeunicellin-based diterpenoids, designated as cladieunicellins M-Q (1-5), were isolated from a Formosan octocoral Cladiella sp. The structures of 1-5 were elucidated on the basis of spectroscopic methods and by comparison of the data with those of the related metabolites. Cytotoxicity of metabolites 1-5 against the human leukemia Molt 4 and HL 60 is also described. Among them, compounds 1, 3 and 5 exhibited moderate cytotoxicity toward Molt 4 cells with IC50 values 16.43, 14.17 and 15.55 µM, respectively. Preliminary SAR (structure activity relationship) information was obtained from these compounds and their analogues.

8-Alkylcoumarins from the fruits of Cnidium monnieri protect against hydrogen peroxide induced oxidative stress damage.

Three new 8-alkylcoumarins, 7-O-methylphellodenol-B (1), 7-methoxy-8-(3-methyl- 2,3-epoxy-1-oxobutyl)chromen-2-one (2), and 3'-O-methylvaginol (3), together with seven known compounds (4-10) were isolated from the fruits of Cnidium monnieri. Their structures were determined by detailed analysis of spectroscopic data and comparison with the data of known analogues. All the isolates were evaluated the cytoprotective activity by MTS cell proliferation assay and the results showed that all the three new 8-alkylcoumarins exhibited cytoprotective effect on Neuro-2a neuroblastoma cells injured by hydrogen peroxide.

Secondary metabolites from the soft coral Sinularia arborea.

Two new 13-hydroxycembrane diterpenoids, arbolides A (1) and B (2), along with a known trihydroxysteroid, crassarosterol A (3), were isolated from the soft coral Sinularia arborea. The structures of new cembranes 1 and 2 were elucidated by spectroscopic methods. Steroid 3 was found to exhibit cytotoxicity toward K562 and MOLT-4 leukemia.

Flexibilisquinone, a new anti-inflammatory quinone from the cultured soft coral Sinularia flexibilis.

A new quinone derivative, flexibilisquinone (1), was isolated from the cultured soft coral Sinularia flexibilis, originally distributed in the waters of Taiwan. The structure of quinone 1 was established by extensive spectroscopic methods, particularly 1D and 2D NMR experiments. In the in vitro anti-inflammatory effects test, quinone 1 was found to significantly inhibit the accumulation of the pro-inflammatory iNOS and COX-2 proteins of the LPS-stimulated RAW264.7 macrophage cells.

Cembrane derivatives from the soft corals, Sinularia gaweli and Sinularia flexibilis.

A new norcembranoidal diterpene, 1-epi-sinulanorcembranolide A (1), and a new cembranoidal diterpene, flexibilin D (2), were isolated from the soft corals, Sinularia gaweli and Sinularia flexibilis, respectively. The structures of new metabolites 1 and 2 were elucidated by spectroscopic methods, and compound 2 was found to significantly inhibit the accumulation of the pro-inflammatory iNOS and COX-2 proteins of the lipopolysaccharide (LPS)-stimulated RAW264.7 macrophage cells. In addition, S. flexibilis yielded a known cembrane, 5-dehydrosinulariolide (3); the structure, including its absolute stereochemistry, was further confirmed by single-crystal X-ray diffraction analysis.

Echinohalimane A, a bioactive halimane-type diterpenoid from a Formosan gorgonian Echinomuricea sp. (Plexauridae).

A new halimane-type diterpenoid, echinohalimane A (1), was isolated from a gorgonian, identified as Echinomuricea sp. The structure of 1 was determined by spectroscopic methods and this compound was found to exhibit cytotoxicity toward various tumor cells and display an inhibitory effect on the release of elastase by human neutrophils. Echinohalimane A (1) is the first halimane analogue from the marine organisms belonging to phylum Cnidaria.

Echinoclerodane A: a new bioactive clerodane-type diterpenoid from a gorgonian coral Echinomuricea sp.

A new clerodane-type diterpenoid, echinoclerodane A (1), was isolated from a Formosan gorgonian coral Echinomuricea sp. The structure of 1 was elucidated by spectroscopic methods. Echinoclerodane A (1) is the first clerodane-type compound obtained from the marine organisms belonging to the phylum Cnidaria. Echinoclerodane A (1) exhibited moderate cytotoxicity toward MOLT-4, HL-60, DLD-1 and LoVo tumor cells and inhibitory effects on the generation of superoxide anion and the release of elastase by human neutrophils.

Lobocrassins A-E: new cembrane-type diterpenoids from the soft coral Lobophytum crassum.

Five new cembrane-type diterpenoids, lobocrassins A-E (1-5), were isolated from the soft coral Lobophytum crassum. The structures of cembranes 1-5 were established by spectroscopic and chemical methods and by comparison of the spectral data with those of known cembrane analogues. Lobocrassin A (1) is the first cembranoid possessing an α-chloromethyl-α-hydroxy-γ-lactone functionality and is the first chlorinated cembranoid from soft corals belonging to the genus Lobophytum. Lobocrassins B (2) and C (3) were found to be the stereoisomers of the known cembranes, 14-deoxycrassin (6) and pseudoplexaurol (7), respectively. Lobocrassin B (2) exhibited modest cytotoxicity toward K562, CCRF-CEM, Molt4, and HepG2 tumor cells and displayed significant inhibitory effects on the generation of superoxide anion and the release of elastase by human neutrophils.

(-)-Hydroxylindestrenolide, a new sesquiterpenoid from a gorgonian coral Menella sp. (Plexauridae).

(-)-Hydroxylindestrenolide (1), an enantiomer of the known sesquiterpenoid, (+)-hydroxylindestrenolide (2), was isolated from a gorgonian coral identified as Menella sp. The structure, including the relative stereochemistry of 1 was established by spectroscopic methods and by comparison the spectral and physical data with those of 2. Sesquiterpenoid 1 exhibited marginal cytotoxicity toward HL-60 and K562 leukemia tumor cells, and displayed a weak inhibitory effect on superoxide anion generation at a concentration of 10 µg/ml by human neutrophils.

Glycerophosphocholine molecular species profiling in the biological tissue using UPLC/MS/MS.

A strategy consisting of a two-phase analytical procedure was used to obtain detailed molecular species composition for glycerophosphocholines (GPCs) profiling in biological tissue using ultra performance liquid chromatography coupled with a triple quadrupole mass spectrometer operating under electrospray mode. In phase one of the analytical procedure, the precursor ion scan was first conducted to obtain the preliminary lipid profile that revealed the composition of the molecular species possessing phosphocholine structure in the biological tissue. In phase two of the analytical procedure, each product ion spectrum obtained for the GPC components in the profile was sequentially acquired for the determination of the molecular structure. A simple guide with high differentiability was proposed for the diacyl-, alkyl-acyl- and alk-1-enyl-acyl-GPC, and related lyso-GPCs molecular structure decision. Total 93 GPCs molecular species were identified in the fetal mouse lung with the relative amounts from 14.39% to less than 0.01% (normalizing by the total GPCs signal). The optimized chromatographic conditions were also proposed in the analytical procedure based on the compromise between the separation efficiency and electrospray signal response. The plate number of the probing GPCs was obviously improved to above 30,000 and the detection limits of the probing GPCs were between 0.002 and 0.016 ng/µL. The practical usability of the analytical procedure has been validated using a study of chemically induced early lung maturation. The metabolic difference between chemically treated and untreated fetal mouse lung was clearly distinguished by the composition of GPCs with several characteristics of molecular structure. The overall results showed that this two-phase analytical procedure was reliable for comprehensive GPC profiling.

Cladieunicellins A-E, new eunicellins from an Indonesian soft coral Cladiella sp.

Five new eunicellin-type diterpenoids, cladieunicellins A-E (1-5), were isolated from an Indonesian soft coral identified as Cladiella sp. The structures of diterpenoids 1-5 were established using spectroscopic methods. Eunicellins 2 and 5 were found to be cytotoxic against DLD-1 and HL-60 tumor cells, respectively, and 3 displayed inhibitory effects against superoxide anion generation by human neutrophils.

Klysimplexins I-T, eunicellin-based diterpenoids from the cultured soft coral Klyxum simplex.

New eunicellin-base diterpenoids, klysimplexins I-T (1-12), were isolated from a cultured soft coral Klyxum simplex. Their structures were elucidated by spectroscopic methods, particularly in 1D and 2D NMR experiments. The absolute stereochemistry of 4 was determined by Mosher's method. Compounds 9 and 12 have been shown to exhibit cytotoxicity toward a limited panel of cancer cell lines. Compounds 2-6, 10 and 11 were found to display significant in vitro anti-inflammatory activity in LPS-stimulated RAW264.7 macrophage cells by inhibiting the expression of the iNOS protein. Compounds 10 and 11 also could effectively reduce the level of COX-2 protein.

Carijoside A, a bioactive sterol glycoside from an octocoral Carijoa sp. (Clavulariidae).

A new bioactive sterol glycoside, 3beta-O-(3',4'-di-O-acetyl-beta-D-arabinopyranosyl)-25xi-cholestane-3beta,5alpha,6beta,26-tetrol-26-acetate) (carijoside A, 1), was isolated from an octocoral identified as Carijoa sp. The structure of glycoside 1 was established by spectroscopic methods and by comparison with spectral data for the other known glycosides. Carijoside A (1) displayed significant inhibitory effects on superoxide anion generation and elastase release by human neutrophils and this compound exhibited moderate cytotoxicity toward DLD-1, P388D1, HL-60, and CCRF-CEM tumor cells.

Cladielloides A and B: new eunicellin-type diterpenoids from an Indonesian octocoral Cladiella sp.

Two new eunicellin-type diterpenoids, cladielloides A (1) and B (2), which were found to possess a 2-hydroxybutyroxy group in their structures, were isolated from an Indonesian octocoral identified as Cladiella sp. The structures of eunicellins 1 and 2 were elucidated by spectroscopic methods. Cladielloide B (2) exhibited moderate cytotoxicity toward CCRF-CEM tumor cells and this compound displayed significant inhibitory effects on superoxide anion generation and elastase release by human neutrophils.

Oxygenated cembranoids from the cultured and wild-type soft corals Sinularia flexibilis.

Two new cembranoids, flexibilisolide A (1) and flexibilisin A (2), along with one known combranoid 5 have been isolated from the cultured soft coral Sinularia flexibilis. Furthermore, two new cembranoids, flexibilisolide B (3) and flexibilisin B (4), along with two known combranoids (5, 6), have been isolated from the wild-type soft coral S. flexibilis. The structures of the new metabolites were determined on the basis of extensive spectroscopic analysis and by comparison of NMR data with those of known compounds. The metabolites 5 and 6 have been shown to exhibit weak cytotoxic activity against MCF-7 cancer cell line.